CN103097468B - The low-titania coating improved - Google Patents

The low-titania coating improved Download PDF

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CN103097468B
CN103097468B CN201180019988.0A CN201180019988A CN103097468B CN 103097468 B CN103097468 B CN 103097468B CN 201180019988 A CN201180019988 A CN 201180019988A CN 103097468 B CN103097468 B CN 103097468B
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coating composition
particle
opacifying property
dispersion agent
coating
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CN103097468A (en
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S·A·惠勒
R·巴考克
C·皮尔斯
G·杰弗森
A·D·伍兹
S·N·艾麦特
J·派雷兹-阿莫罗斯
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Akzo Nobel Coatings International BV
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/028—Pigments; Filters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/45—Anti-settling agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres
    • C08L2205/20—Hollow spheres
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Abstract

There is the water-based paint compositions of the PVC of 78 to 85%, unless otherwise specified, based on the total solids volume content of dry coating, described coating composition comprises: a) opacifying property pigment particles, it comprises: i) 3 to 10% titanium dioxide, ii) 0 to 20% hollow polymeric particle; B) non-opacifying property extender particles, it comprises: i) magnesium calcium carbonate, and/or ii) calcium carbonate, and/or iii) nepheline syenite, and/or iv) kaolin, wherein i)+ii)+iii)+iv)=40 to 80% and iv) be 0 to 20%; C) polymer binder particle, its Fox? Tg calculated value is 5 to 25 DEG C, has the acid number of 15 to 65mgKOH/g polymkeric substance, and wherein this polymer particle derived from propylene acid mono, and optionally comprise vinylbenzene and/or its derivative further; D) dispersion agent, it has at least 3500 daltonian weight-average molecular weight, and select on following basis: based on the Weight computation of titanium dioxide and extender particles, the dispersion agent demand of the opacifying property pigment particles except hollow polymeric particle a) and the mixture of extender particles b) is greater than 0.35 % by weight, e) fugitive agglomerated solvent, wherein said composition is not containing non-fugitive agglomerated solvent.

Description

The low-titania coating improved
The present invention relates to the colored paint composition that energy content reduces, be especially low to moderate the colored paint of gloss medium, also referred to as sub-light or sheen (softsheen) paint.It is 78 to 85% in particular to pigment volume content and has the paint of the gloss being less than 30% when measuring for 85 °.
The titanium dioxide TiO of light color colored paint usually containing high-content 2.This is because such light appearance mainly white and add a small amount of non-white.Relative to paint in use typical adhesive, titanium dioxide because of its high refractive index but the whiteness of the best source.Regrettably, TiO 2need large energy could extract from ground (ground) and then purify.In fact, in high pigment volume content (PVC) paint of known light color/light color (sub-light white such as described below and sub-light pastel shade), for realizing the high TiO of required color and opaqueness 2content (usual 10 to 20 volume %) be paint total energy content mainly facilitate factor.
Energy content refers to extraction, refines and manufactures the energy needed for composition forming paint; The energy required with manufacturing paint itself.
Because the burning of most of energy by fossil oil generates, high energy content causes high Carbon emission usually---and therefore use another to measure " recessive CO 2" instruction energy content.
The most serious commentator also generally admits the disadvantageous effect of this discharge to global environment, especially climate change.Therefore need to reduce the energy consumed in the production of this paint.
A kind of method reduces the TiO of paint 2content.But this only reduces the opaqueness of dry coating, although each dried lacquer coating also can have the energy content of reduction, extra cost is needed to realize opaqueness.Therefore, any benefit is all lost or is at least significantly reduced.Other methods are by some or all of TiO 2change pigment extender into, such as chalk.Although the energy that the purifying of this kind of extender needs is less than TiO 2, but the tackiness agent that the lower refractive index of this kind of extender uses in closely painting.Therefore, they are unlike TiO 2scattered light like that well, in order to compensate the TiO of reduction 2amount, must add to more extenders in paint to realize correct color and opaqueness.But this increases PVC further, finally reach air and be trapped within degree in dry paint.Although which increase opaqueness, it also causes poor moisture-resistant scrubbing character usually.
A kind of possible mode breaking away from this predicament uses calcined clay, because it has good opaqueness, and do not damage scrub resistance.But manufacturing calcined clay needs clay to be heated to 1000 DEG C, lot of energy thus.This is obviously significantly not energy-conservation and be not therefore preferred selection.
US Patent No. 4,277,385 coating compositions disclosing the PVC with 75 to 85%, and instruct further, for avoiding the crackle in high PVC paint film, this formula should not contain non-opacifying property mineral dye (another title of extender), when especially they being replaced to non-film solid polymer particles.But, do not have to attempt making the TiO in these formulas 2content minimizes, and so there is no overcome high energy content and high CO 2the problem of discharge.
European patent application EP 0113435 describes the TiO under the PVC of 20 to 80% with reduction 2the water-miscible paint of content.The mixture which teach the larger Opacifying polymers particle that use comprises coloured blister polymeric beads and has micropore (but not having pigment) replaces TiO 2, keep gloss/scrub resistance simultaneously.But as pointed out in this application, coloured blister polymeric beads itself is containing TiO 2, and therefore significantly increase TiO 2content.This is almost helpless to the total energy content reducing paint.Coloured blister polymeric beads is both containing TiO 2again containing the polymer particle of micropore.
Therefore, need the coating compositions improved, it has the TiO of reduction 2content and therefore low energy content, and also there is good opaqueness and good moisture-resistant scrubbing character simultaneously.
Correspondingly, provide the water-based paint compositions of the PVC with 78 to 85%, unless otherwise specified, based on the total solids volume content of dry coating, described coating composition comprises:
A) opacifying property pigment particles, it comprises
I) 3 to 10% titanium dioxide
Ii) 0 to 20% hollow polymeric particle
B) non-opacifying property extender particles, it comprises
I) magnesium calcium carbonate and/or
Ii) calcium carbonate and/or
Iii) nepheline syenite and/or
Iv) kaolin
Wherein i)+ii)+iii)+iv)=40 to 80% and iv) be 0 to 20%
C) polymer binder particle, its FoxTg calculated value is 5 to 25 DEG C, has the acid number of 15 to 65mgKOH/g polymkeric substance, and wherein this polymer particle derived from propylene acrylic monomer, and optionally comprise vinylbenzene and/or its derivative further
D) dispersion agent, it has at least 3500 daltonian weight-average molecular weight, and select on following basis: measured by following method, based on the Weight computation of titanium dioxide and extender particles, the dispersion agent demand of the opacifying property pigment particles except hollow polymeric particle a) and the mixture of extender particles b) is greater than 0.35 % by weight
E) fugitive agglomerated solvent
Wherein said composition is not containing non-fugitive agglomerated solvent.
Preferably, pigment volume content is 79 to 85, more preferably 80 to 85, more more preferably 80 to 84, most preferably 81 to 83%.Actual PVC and a) and any difference b) between total amount be made up of such as other non-opacifying property pigment extender undefined.
Preferably, described opacifying property pigment particles is white.
More preferably, described opacifying property pigment particles is by TiO 2form with Hollow Latex Particles.Again more preferably, described opacifying property pigment particles is only by TiO 2form.By the TiO that known chloride process is made 2be preferred in the present invention, because its energy manufacturing needs is lower, and in coating, therefore introduce less recessive CO 2.
Titanium dioxide is preferably rutile form, because anatase octahedrite is the scattering object compared with poor efficiency, therefore needs manyly could realize identical opaqueness.
Preferably, TiO 2account for 3 to 9 of composition, more preferably 3 to 8, more more preferably 5 to 8, again more preferably 6 to 8, more preferably 5 to 7, most preferably 6 to 7 volume %.
The particle of hollow polymeric (preferably spherical) also can be used for providing White-opalescent degree.Suitable such particle contains the space of 30 to 50 volume % of particle.This particle can with the form of water dispersion with trade(brand)name Ropaque tMobtain.But, composition preferably containing the spherical white pigment of this polymeric hollow being less than 10 volume % because they significantly increase the energy content of paint.In addition, they are often for dried dry paint provides undesired gloss.More preferably, said composition is not containing such hollow polymeric particle.
Similarly, calcined clay---a kind of white pigment, can be used as TiO 2partial substitute.But, because the production of calcined clay itself is energy-intensive, therefore must the careful amount limiting calcined clay used in formula.In order to farthest energy-conservation, this coating composition is not preferably containing calcined clay.But, preferably can use the calcined clay of maximum 30 volume %, more preferably 5 to 20 volume %, most preferably 10 to 15 volume %.Also coloured blister polymeric beads is preferably avoided.
Certainly, except other opacifying property pigment particles described, can also add in composition of the present invention, to produce light color/light color by such coloured opacifying property pigment by different tone as discussed in more detail below.
Non-opacifying property extender particles refers to the inorganic particulate with the same or similar refractive index with polymer binder.Opacifying property intensity due to microparticle material is the index difference of this material and its dispersion medium and the result of granularity thereof, these extenders are regarded as non-opacifying property dose substantially, see PaintandSurfaceCoatings-theoryandpractice, 35 to 37 page, R.Lambourne edits and JohnWileyandSons publishes. and this is not say that they are helpless to opaqueness completely, but and TiO 2compare its effect little.
Extender is not pure white usually, and can provide some grey or yellow tone for coating.
The suitable example of non-opacifying property extender particles comprises magnesium calcium carbonate, calcium carbonate, nepheline syenite, kaolin, talcum, silicon-dioxide, diatomite, mica and calcium sulfate.This non-opacifying property extender particles is preferably selected from magnesium calcium carbonate, calcium carbonate, nepheline syenite and kaolin.This non-opacifying property extender particles is preferably selected from the list be made up of magnesium calcium carbonate, calcium carbonate, nepheline syenite and kaolin.They are more preferably selected from the group be made up of magnesium calcium carbonate, calcium carbonate and kaolin.
The mineral being referred to as rhombspar are magnesium calcium carbonate CaMg (CO 3) 2convenience and cost effectively originate.Rhombspar is the preferred source for magnesium calcium carbonate of the present invention.It can obtain with the powder type of different mean particle size.
The suitable form of calcium carbonate comprises calcite, comprises precipitated calcite.SocalP3 is the example of the suitable precipitated chalk of calcite form.Suitable water-ground limestone is Omyacoat850OG.
Nepheline syenite can be used for partially or completely substituting calcium carbonate.
Kaolin Al 2si 2o 5(OH) 4it is the clay of a type.The kaolin that (based on dry coating) adds higher than 20 volume % in the composition causes poor moisture-resistant scrubbing character.In addition, under kaolin content high like this, dope viscosity is too high so that cannot use that conventional application techniques (such as roller or brush) is simple and easy to be spread, and paint cannot be made to flow to produce acceptable smooth finish.Advantageously, kaolinic amount should be 0.5 to 20, and more preferably 5 to 15, most preferably 6 to 12 volume %.
Non-opacifying property extender particles is preferably 50 to 75 of dry coating, and more preferably 50 to 70, most preferably 55 to 67 volume %.
Advantageously, dry coating total solids volume content 20 to 50% should comprise median particle d 50the extender particles of≤2 microns.This guarantees TiO 2particle fully separates, to make scattering effectively and therefore to optimize opaqueness.
As the granularity of d50 diameter citation extender.This means that the particle of 50 volume % is lower than this diameter.
Tackiness agent comprises the water dispersion of polymer binder particle, is often called latex.This dispersion more preferably uses emulsion polymerization manufacture.
For the sake of simplicity, word " polymkeric substance " is in this manual for containing homopolymer and the multipolymer comprising two or more monomeric variant.
The polymkeric substance forming this binder particles is preferably Styrene-acrylic copolymer or pure acrylic acid class.
Pure acrylic acid class refers to this polymkeric substance only derived from the monomer being selected from acrylate and methacrylic ester and acid itself.
Styrene And Chloroalkyl Acrylates refer to some vinylbenzene and/or its can copolymerization derivative copolymerization in this polymkeric substance.Suitable such styrene derivatives comprises alpha-methyl styrene and Vinyl toluene.
More preferably styrene acrylic polymer particle, because these need minimum energy manufacture compared with pure acrylic acid class, most preferably, the polymer binder in the present invention is derived from vinylbenzene, butyl acrylate and can the acid of copolymerization.Described can the acid of copolymerization be most preferably vinylformic acid and/or methacrylic acid.
Calculate based on solids content in volume, the binder content of coating is preferably 5 to 20%, and more preferably 5 to 15, most preferably 8 to 15%.
Suitable acrylic monomer comprises the alkyl ester of acrylic or methacrylic acid, such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, ethyl propenoate, butyl acrylate, Ethyl acrylate, n-octyl, lauryl methacrylate, 2-Ethylhexyl Methacrylate, vinylformic acid ester in the ninth of the ten Heavenly Stems, decyl acrylate, benzyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, isobornyl methacrylate, the hydroxy alkyl ester of same acids, as vinylformic acid 2-hydroxyl ethyl ester, HEMA and methacrylic acid 2-hydroxypropyl acrylate.
The acid number of described polymkeric substance is preferably 15 to 60, and more preferably 15 to 55, more more preferably 15 to 45, the most preferably non-volatile polymkeric substance of 16 to 30mgKOH/g.Acid number lower than 15mgKOH/g polymkeric substance produces the dried lacquer of poor moisture-resistant scrubbing character, and often reduces the moisture-resistant scrubbing character of dried lacquer higher than 65mgKOH/g polymkeric substance.
Be copolymerized to by acid functional monomer in the polymkeric substance of constituent particle and change acid number.Suitable such monomer comprises vinylformic acid, methacrylic acid and toxilic acid or its acid anhydride.Acid used is preferably vinylformic acid.
The polymkeric substance that mean particle size is not more than 0.3 micron is preferred, because the particulate constituent of described composition is bonded together by better.
The equal mean particle size of number of this polymer particle is preferably 0.05 to 0.30 micron, more preferably 0.07 to 0.15 micron, most preferably 0.08 to 0.14 micron.This numerical value refers to the diameter of particle.Smaller particle size is preferred, because it causes the scrub resistance of improvement, this is particularly important under high PVC of the present invention.
The glass transition temperature Tg of telomerized polymer tackiness agent can be carried out by the selection of monomer and the relative quantity of each monomer forming this polymkeric substance.It is preferably 6 to 21 DEG C, more preferably 6 to 19 DEG C, more more preferably 6 to 16 DEG C ....
For avoiding query, unless otherwise specified, any Tg mentioned in this manual refers to FoxTg calculated value.
When using the polymkeric substance of higher Tg, need more coalescent and/or plastification solvent could be formed under the normal room temperature of about 20 to 25 DEG C in polysilazane coating film.The polymkeric substance of lower Tg is preferred, because these can, by the effective film forming of solvent of lower aq, make the volatile organic content of this paint and the energy content of this paint all remain on minimum level thus.
Pigment dispersing agent comprises hydrophilic segment and hydrophobic part usually, and according to the character of dispersion medium and surface of pigments, a part has comparatively high affinity to surface of pigments, and another part has comparatively high affinity to dispersion medium.The stabilising dispersions of dispersion pigment in media as well can be produced thus.
In the present invention, dispersion agent is needed to make non-polymeric opacifying property pigment (comprising any coloured pigment) and non-opacifying property extender particles dispersion and stablize.The weight-average molecular weight of dispersion agent is necessary at least 3500 dalton, and based on the Weight computation of inorganic opacifying property pigment and non-opacifying property extender particles, is necessary for is greater than 0.35 % by weight non-volatile dispersion agent according to the dispersion agent demand of following test method.Do not meet these two dispersion agents required and produce the unacceptable dry film of moisture-resistant scrubbing character.
The weight-average molecular weight of this dispersion agent is preferably at least 4000, and more preferably 5000, most preferably 6000 dalton.The upper limit of weight-average molecular weight is preferably 50000 dalton, and more preferably 40000, more more preferably 30000, more more preferably 20000, most preferably 15000 dalton.The most preferred molecular-weight average of this dispersion agent is 3500 to 20000 dalton.
Dispersion agent demand is the dispersion agent minimum quantity producing MV minium viscosity when in the dispersion of adding non-polymeric opacifying property pigment particles (comprising any coloured pigment) and extender to.MV minium viscosity refers to adds the further reduction that dispersion agent (usually in the form of a solution) does not cause viscosity.
The appropriate method of assessment dispersion agent demand comprises the steps: i) to be added to gradually by dispersion agent in the water dispersion of non-polymeric opacifying property pigment (comprising any coloured pigment) and extender particles, and the viscosity of monitoring gained mixture is to determine MV minium viscosity, and ii) minimum quantity for reaching the dispersion agent that MV minium viscosity is added is defined as dispersion agent demand.
Preferred method is described in testing sequence.
Be applicable to dispersion agent of the present invention and comprise Orotan tM681, Orotan tM731 and Orotan2002.These have separately and are greater than 3500 daltonian molecular weight, and the Pass Test of dispersion agent demand.DispexHDN is applicable to another dispersion agent of the present invention, and manufactured business is described as " the hydrophobic sodium salt of acrylic copolymer ".
The method of assessment dispersion agent demand is described below.
Usually by adding in white paint by a small amount of various coloured pigment of masterbatched dispersion (also referred to as colorant or tinting material) form, light color is manufactured thus.
In order to realize required scrub resistance, importantly, agglomerated solvent is fugitive, that is, it must leave paint film.Polymkeric substance according to solvent and tackiness agent forms, and this may occur very fast or use a couple of days possibly.As guidance, we find, as the Texanol of coating (2 % by weight Texanol are in liquid lacquer) only containing 0.06 % by weight in this film after dry 24 hours under dry environment condition of embodiments of the invention 1, only containing 0.01 % by weight after other 6 days.
Preferably, the FoxTg calculated value of this polymkeric substance can be down to-10 to-80 DEG C by this fugitive agglomerated solvent, is more preferably down to-10 to-60 DEG C, is more more preferably down to-10 to-40 DEG C, be most preferably down to-10 to-20 DEG C.Calculate based on liquid preparation, preferably use maximum 4 % by weight, more more preferably maximum 3 % by weight, more more preferably maximum 2 % by weight, more more preferably maximum 1%, most preferably maximum 0.5 % by weight realize this reduction.
The degree that the FoxTg calculated value of particular polymers reduces by agglomerated solvent can calculate according to formula 1:
1/Tg=V p/ Tg p+ α V s/ Tg sformula 1
Wherein Tg pand Tg sthe second-order transition temperature of polymkeric substance and solvent respectively
Tg is the second-order transition temperature of Plasticising system
V pand V sthe volume fraction of polymkeric substance and solvent respectively
α is the factor of the little change that plasticizing efficiency is described, is assumed to 1 for the purpose of the present invention.
Suitable fugitive agglomerated solvent comprises Lusolvan tMthe diisobutyl ester of the mixture of FBH(dicarboxylic acid), Lusolvan tMthe diisobutyl ester of the mixture of PP(dicarboxylic acid), Loxanol tMeFC300(ol ester), ButyCarbitol tM, ButylCellosolve, Dowanol tMePh(ethylene glycol phenyl ether), Dowanol tMpPh(propylene glycol phenyl ether), DowanolTPnB(tripropylene glycol n-butyl ether), tMdowanolDPnB, DBE_9 tM(mixture of refining Methyl glutarate (gluterate dimethyl ester) and Succinic acid dimethylester), EastmanDB tMsolvent, EastmanEB tM(ethylene glycol monobutyl ether), Texanol tM(2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate), Dapro tMfX511, Velate tM262, Arcosolve tMdPNB, Arcosolve tMtPnB and benzylalcohol.
The list of solvent and their second-order transition temperature is found in 29 ththe article " AnAppliedApproachtoFilmFormation " of JWTaylor and TDKlots that AnnualWaterborne, HighSolidsandPowderCoatingsSymposium deliver.
List some representative second-order transition temperatures of solvent below:
Thickening material is used to control viscosity and the rheological of said composition in the coating composition.Carboxymethyl cellulose type is comprised, as Blanose for suitable rheology modifier of the present invention tM731; Natvosol, as Natrosol tM250 and Tylose tMh grade; The Natvosol of hydrophobically modified, such as Natrosol tMplus and Tylose tMhX grade; Ethyl and ethyl-methyl Natvosol, such as Beromocoll tMeHM grade; Nonionic synthesis associative thickener (NSAT ' s), such as Acrysol tMrM825, Acrysol tMsCT275, Acrysol tMrM2020, Aquaflow tMnHS300, Coapur tM830W, Rheolate tM450, Bermodol tMpUR grade; Alkali swelling property milk sap (HASE) thickening material of hydrophobically modified, such as Acrysol tMtT935, Acrysol tMdR73, CibaRheovis tM; Alkali swelling property synthetic thickening agent (ASST).
NSAT, HASE, ASST and HEUR type thickening material is more preferred than cellulase type.
Usually high TiO is being needed 2benefit of the present invention is advantageously realized in the colored paint composition of content.Such color is grey and light-coloured coating, is often referred to as light color or light color, and certain white.
Known Y, C can be used *, h *system definition these and all colours.Within the system, any color can represent as follows:
I. tone, by h *describe
Its colourity of ii, C *,
Iii. its luminous reflectance factor value, Y
CommissionInternationaledel'Eclairage (CIE) scientifically defines these terms [see " InternationalLightingVocabulary ", 4th edition, the IEC/CIE017.4-1987.ISBN9783900734077 of publication].
For avoiding any query, unless otherwise specified, in this specification sheets, any painting color mentioned refers to the color of this coating when drying.
Tone is that color is measured close to red, yellow, and green and blue in which kind of degree.It is described by the hue-angle of 0 to 360 °, and wherein this angle specifies the position of this tone in the color space, and wherein red, yellow, and green and indigo plant are respectively the angle of 0,90,180 and 270 °.Angle between these " basic points " refers to middle shade, and the such as hue-angle of 45 ° is reddish yellow (orange) look.
Colourity is measuring of colour strength (that is, it being the degree of light color/light color or strong color or certain color between them).Colourity can be the value of 0 to 100, and high value refers to stronger color.Colourimetric number be 0 color be positioned on the axle from black to white " neutrality " ash.
Luminous reflectance factor value is measuring of the colour brilliance of perception, is 0 to 100,0 to represent black, and 100 representatives are white.
Fig. 2 shows Y, the simplicity of illustration of C*, h* system.Its color space being presented at about mid point of luminous reflectance factor value Y scope divides.Y-axis is from 0 to 100.Red, yellow, and green and blue their appropriate location be presented in hue circle.C* axle is from 0 of initial point to 100 of all strong points.In each Y value, the Further Division of tone is association, represents more shallow and comparatively dark colour.In the dark of Y scale and shallow end, color is all more weak, and therefore colourity is inevitably low.Therefore, the color space is often depicted as spheroid, although in fact its shape is more as irregular cylinder.
Use CIE symbolic notation, benefits from grey of the present invention most or light composition can be defined as being those colors meeting following standard, comprises white:
C*<C criticalformula 1
Y>mC*+35 formula 2
Wherein m and C criticaltake off the value in table 1.
Table 1
Higher than C criticalvalue, then colour strength is too high so that cannot be regarded as light color.
M and C under middle shade angle modulation criticalvalue can be calculated by linear interpolation method.
According to this table, the C under any given tone can be calculated *and Y, clearly identify white, grey or light color/light tone thus.
Chrominance C *be less than about 5 and the coating of Y value about 95 by Human Perception for white.
Can by the C of any color of luminous reflectance factor curve calculation of the color using spectrophotometer to record according to the explanation of manufacturers *, Y and h *value.Suitable spectrophotometer is DatacolorSpectraflashSF600.
Preferably, dry paint composition coincidence formula 1 and 2 of the present invention.This dry paint composition more preferably has the colourity being less than 5 and the Y value being greater than 85.
Preferably, when measuring for 85 °, the gloss value of dry coating is less than 30%, is more preferably less than 20%, then is more preferably less than 10%, then is more preferably less than 5%, and most preferably 2 to 8%.
This coating composition also can containing other composition for coating standard, such as wax, rheology modifier, tensio-active agent, antifoams, tackifier, softening agent, linking agent, glidant, biocide and clay.
In another aspect of this invention, provide, with composition coating of the present invention, there is the goods on surface or the method for structure, comprise the steps: at least one liquid level by brush, roller, pad or this coating of spray application, and make this layer of drying and/or sclerosis.
In another aspect of this invention, provide the goods or structure with the surface be coated with composition of the present invention.
Following compositions is used to prepare embodiment.
Tioxide tMtR92 is the TiO of rutile form 2(density is 4.05g/cm 3), can available from HuntsmanTioxideEuropeLtd, Hartlepool, Cleveland Britain.
Microdol tMh200 and H600 is that (density is 2.85g/cm to rhombspar 3) and can available from Omya.OmyaHouse, Derby, Britain
Socal tMp3 is that (density is 2.70g/cm to precipitated chalk 3) and can available from Solvay, Rheinberg, Germany.
ChinaClaySupreme-kaolin (density 2.60g/cm 3) can available from Imerys.
Ropaque tMultraE is that (density is 0.591g/cm for 30% non-volatile dispersion of hollow polymeric spherolite 3) and can available from RohmandHaas, Philadelphia, the U.S..
Steabright tMbe can available from RioTintoPLC, London, (density be 2.78g/cm to the talcum of Britain 3).
Texanol tMcan available from EastmanChemicalCompany, Tennessee, the ester alcohol coalescing agent of the U.S..
TegMer tM804 is can available from the TEG ester of Hallstar, 120SouthRiversidePlaza, Suite1620, Chicago, Illinois60606, USA.
Orotan tM731A is can available from the pigment dispersing agent of Rohm & HaasPhiladelphia, USA (25 % by weight non-volatile matters; The density of non-volatile matter is 1g/cm 3).
Disponil tMa1580 is tensio-active agent (80 % by weight non-volatile matters; The density of non-volatile matter is 1.00g/cm 3) and can available from CognisDeutschlandGmbH & Co.KG.POBox130164, Germany.
DispexN40 is can available from the dispersion agent of Ciba.
Dispelair tMcF823 is defoamer (60 % by weight non-volatile matters; The density of non-volatile matter is 1.00g/cm -3) and can available from BlackburnChemicalsLtd, WhitebirkIndustrialEstate, Blackburn, Britain.
Blanose tM7M31CSCS9554(density 1.59g/cm 3) can available from HerculesGmbH, Dusseldorf, Germany.
ActicideCHR0107 is can available from ThoratWinchamAvenue, Wincham, Northwich, Cheshire, English biocide.
Aquaflow tMnHS300(23 % by weight non-volatile matter; The density of non-volatile matter is 1.00g/cm 3) be that thickening material/rheology modifier also can available from HerculesGmbH, Dusseldorf, Germany.
ChinaClaySupreme(density is 2.60g/cm 3) can available from Imerys.
Latex1 is the styrene/acrylic butyl ester/Sipacril 2739OF with Tg10 DEG C and acid number 23.5mgKOH/g polymkeric substance and 50 % by weight solid contents.
Latex2 is the styrene/acrylic butyl ester/Sipacril 2739OF with Tg-10 DEG C and acid number 23.5mgKOH/g polymkeric substance and 50 % by weight solid contents.
Latex3 is the styrene/acrylic butyl ester/Sipacril 2739OF with Tg10 DEG C and acid number 11mgKOH/g polymkeric substance and 50 % by weight solid contents.
Use following test method:
the molecular weight of dispersion agent
Use AqueousGPC measurement device molecular weight.
Equipment used and condition are:
Post: from 2 × 30cmTSKGMPWXLGPC post of Tosoh
Eluent: 0.3M SODIUMNITRATE, 0.01M sodium phosphate, uses 0.1MNaOH by pH regulator to 7.5
Flow velocity: 1.0ml/min
Detector: Waters410 differential refractive index detector.
Software: WatersMillennium32v3.05.01
Rectify an instrument with the dextran standard specimen covering 342-401000g/mol scope.
Sample is prepared by diluting 0.1 gram and filter through 0.45 micrometer PVDF membrane in 10 milliliters of eluents.
Volume injected is 100 microlitres.
opaqueness (contrast ratio)
According to BS3900-D4 measurement for opaque degree.
At least 90% is considered to acceptable.
The relation of the opaque degree of the opaqueness recorded and naked eyes perception is not linear.Therefore, the little difference of the opaqueness recorded is regarded as much bigger difference by naked eyes.
glossiness
Glossiness is measured according to BSENISO2813, BS3900-D5.
moisture-resistant scrubbing character
Use the scrub resistance of 200 period measurement dry films according to BSENISO11998, change is with milli gram/cm recording loss.The loss being less than 6 milli gram/cm removal amounts is acceptable.
shear viscosity
Be used in 10,000s -1the ICI cone and plate viscometer (can available from ResearchEquipmentLondonLtd, London, TW25NX) of lower operation measures shear viscosity at 25 DEG C.
rotothinner viscosity (paint)
Use is furnished with about 562rpm(that this is equivalent to about 250s -1shearing rate) the Rotothinner viscometer (can available from SheenInstrumentsLtd, Kingston-upon-Thames, Surrey, UK) of normal disc rotor that rotates measures moderate shear viscosity at 25 DEG C.
the granularity of extender
Mastersizer is used to measure the granularity of extender according to ISO13323part1 & 2.
measure the method for dispersion agent demand
Experimental basis is added to by dispersion agent in the water dispersion of inorganic opacifying property pigment and non-opacifying property extender particles gradually, measures viscosity until reach MV minium viscosity simultaneously.For the amount (being expressed as % by weight of the non-volatile dispersion agent calculated based on particle weight) realizing the dispersion agent that this viscosity is added is dispersion agent demand.Component amount used takes from % by weight preparation.
Following method is used to measure dispersion agent demand:
1. be arranged to add about 150 grams of water in the 500 cubic centimetres of painted metal tanks stirred with the high speed agitator being furnished with 40 to 50mm blade (HSD).Definitely measuring certainly in formula of water.
2. add expection final quantity about 50 to 65 % by weight candidate's dispersion agent---this may need the first titration to draw the initial estimated value of dispersion agent demand, thus carry out more accurately secondary measure.
3., while stirring under about 200rpm, all the components except opacifying property pigment, non-opacifying property extender particles, thickening material, biocide and tackiness agent is added in the mixture in step 2.Further stirring 2 minutes.
4. add non-opacifying property extender particles and the non-polymeric opacifying property pigment except any coloured opacifying property pigment.In adding procedure, stirring is increased to about 2500rpm or requirements, to keep the vortex in this tank.The solid content of this mixture should be about 70 % by weight in this stage.
5. use the Rotothinner viscosity meter viscosity of being furnished with the ball rotor of 562rpm rotation.For simplicity, the viscosity in this stage should be about 6.0 to 7.0Pa.s.Some trial and errors may be realize that this is necessary.If it is so high so that cannot stir, dispersion agent and/or water can be added.For the combination of some extenders, viscosity may be too high or too low, in this case, from step 1, uses more or less water on demand specifically.
6. in this mixture, add more multi-dispersant use HSD to be mixed into.
7. repeating step 5 and 6, the interpolation before viscosity-modifying when adding dispersion agent until further is less than.
8. by drawing the figure of the dispersion agent (be expressed as % by weight dispersion agent, calculate based on the weight of opacifying property pigment particles and the weight summation of non-opacifying property extender particles) that viscosity vs adds, assessment dispersion agent demand.The non-volatile dispersion agent minimum quantity realizing MV minium viscosity is regarded as dispersion agent demand.
Candidate's dispersion agent should use with non-volatile content high as far as possible, to avoid by simply diluting the viscosity degradation caused.
Rotothinner viscometer (reference number 455N/15) can available from SheenInstruments, 2, GattonParkBusinessCentre, WellsPlace, Redhill, Surrey, RH13LG
Such as, the following dispersion agent demand (for Orotan731) measuring embodiment 1:
1. be arranged to add 128 grams of water in the 500 cubic centimetres of painted metal tanks stirred with the high speed disperser being furnished with 40 to 50mm blade (HSD).
2. add 5.3 grams of Orotan731 as 25% actives supply wherein.
3. then Texanol (17.7g), DisponilA1580 (4.42g) and DispelairCF823 (1.15g) are added in the mixture in step 2, and stir 2 minutes at 200 rpm.
4., while slowly stirring, add the premix adulterant of MicrodolH600 (75.2g), SocalP3 (110.57g), ChinaClaySupreme (48.65g), Steabright (75.2g), MicrodolH200 (75.2g) and TioxideTR92 (57.5g).In adding procedure, agitator speed be increased to 2500rpm and keep 5 minutes.
5.Rotothinner viscosity is measured as 6.5Pa.s.
6. then add other 0.87 gram of Orotan731(25% actives), this mixture is disperseed other 2 minutes under 2500rpm, and to record Rotothinner viscosity be 5.4Pa.s.
7. this repeats until reach the viscosity of 2.2Pa.s.As can be seen from the curve in Fig. 1, add dispersion agent and exceed this MV minium viscosity point, to assess dispersion agent demand.
For Orotan731, for reaching MV minium viscosity, add 8.76 grams of dispersion agents altogether.Dispersion agent demand is 0.50 % by weight.
Need to illustrate, in addition to water, composition is relative to each other correct ratio.The water-content reduced allows to detect viscosity minimum value.
Fig. 1 shows the viscosity of the various dispersion agent graphic representation relative to the non-volatile dispersion agent added.
Line A represents the curve of DispexN40 (dispersion agent demand 0.12 % by weight)
Line B represents the curve of Potassium tripolyphosphate
Line C represents the curve of Orotan731 (dispersion agent demand 0.50 % by weight)
Line D represents the curve of StrodexPK-80A
Line E represents the curve of Orotan681 (dispersion agent demand 1.50 % by weight)
Line F represents the curve of NuosperseFA-196.
Wherein, only have Orotan681 and Orotan731 to be applicable to the present invention because they to be only molecular weight be greater than Mw.3500 dalton and dispersion agent demand is greater than 0.35 % by weight two kinds.
Embodiment
Now by the present invention of following embodiment illustration.
The embodiment of numbering is the present invention, comparative example letter designation.In all cases, % by weight preparation relates to liquid lacquer, and volume % relates to dry coating.
Use following method manufacture paint in each case.
the mill base stage
Use 5 liters of metal dispersion containers, load the Dispelair of water (1), Texanol, Orotan or Dispex, Disponil, Acticide and half amount.Under container is placed in the high speed disperser being furnished with saw-toothed blade.Low rate mixing, makes not observe splashing.Add MicrodolH200 and H600, SocalP3, ChinaClaySupreme, Steabright and TioxideTR92, slow running 2 minutes, then adds Blanose thickening material.Along with paint retrogradation, slowly improved speed through 5 minutes.Device should with about 2500r.p.m.(according to volume) run, but do not splash.Stir 30 minutes again.Midway stop gear, guarantees do not have pigment to be adhered to container side/bottom manually to stir.Device is restarted at a high speed, reduce to after 30 minutes at a slow speed.By brushing out the dispersion state checking mill base on card, to check particle.If particle amount can accept, add water (2) and rerun 2 minutes, then turning off agitator.
The water inventory shown in Example formulations is ratio: water (1): water (2): water (3)=45.5:30.3:24.2.
the paint stage
Latex1 is loaded in the suitable container of size, and under being placed in the agitator being furnished with blade.
Load Ropaque, residue Dispelair, the mill base as above prepared, water (3) and Aquaflow.Along with the volume in container improves, regulate agitator speed, carefully avoid splashing.
15 minutes are stirred again under low speed (about 500r.p.m).
Embodiment 1 and A
Embodiment 1 and A are substantially identical except PVC difference.Comparative example A does not have by wet scrub test under PVC86.
Aforementioned formula 1 is used to calculate the Tg of polymer binder when there is agglomerated solvent
1/Tg=V p/ Tg p+ α V s/ Tg sformula 1
The Tg of Texanol is-84 DEG C.
Only calculate volume fraction based on polymkeric substance and solvent.
Therefore for embodiment 1, the gross weight % of polymkeric substance is 50% of 3.25(6.5), solvent is 2.00.The proportion of polymkeric substance and solvent is respectively 1.08 and 0.95, and therefore volume fraction is respectively 0.15 and 0.85.Therefore the Tg of this polymkeric substance when there is Texanol is-9.5 DEG C.
Embodiment 2 and B
They are substantially identical except ChinaClaySupreme (kaolin) content.Comparative example B does not have by wet scrub test under the kaolin content of 28.52 volume %.
Embodiment 3 and C
Except the latex difference in these two embodiments, embodiment 3 is identical with C.Use the comparative example C of the latex of Tg-10 DEG C not by wet scrub test.
Embodiment 4 and D
The impact of latex acid number
Use the comparative example D of the latex 3 of AV11mgKOH/g polymkeric substance not by wet scrub test.
Embodiment 5 and E
Use the impact of the dispersion agent of the dispersion agent demand producing <0.45 % by weight
The dispersion agent demand of comparative example E is <0.45 % by weight.
Embodiment 6 and F
The impact of non-fugitive agglomerated solvent
Embodiment 7
Not containing the coating of hollow polymeric particle
Standard specimen (i) and (ii)
Standard specimen (i) and (ii) show, under PVC<78%, can use any dispersion agent and not damage wet scrubbing character.In standard specimen (ii), DispexN40 used does not meet the dispersion agent demanding criteria of <0.35 % by weight, but this coating have passed wet scrub test.

Claims (23)

1. have the water-based paint compositions of the pigment volume content of 78 to 85%, based on the total solids volume content of dry coating, described coating composition comprises:
A) opacifying property pigment particles, it comprises
I) 3 to 10% titanium dioxide
Ii) 0 to 20% hollow polymeric particle
B) non-opacifying property extender particles, it comprises
I) magnesium calcium carbonate and/or
Ii) calcium carbonate and/or
Iii) nepheline syenite and/or
Iv) kaolin
Wherein i)+ii)+iii)+iv)=40 to 80% and iv) be 0 to 20%
C) polymer binder particle, its FoxTg calculated value is 5 to 25 DEG C, has the acid number of 15 to 65mgKOH/g polymkeric substance, and wherein this polymer particle derived from propylene acrylic monomer, and optionally comprise vinylbenzene and/or its derivative further
D) dispersion agent, it has at least 3500 daltonian weight-average molecular weight, and select on following basis: based on the Weight computation of titanium dioxide and extender particles, the dispersion agent demand of the opacifying property pigment particles except hollow polymeric particle a) and the mixture of extender particles b) is greater than 0.35 % by weight
E) fugitive agglomerated solvent
Wherein said composition not containing non-fugitive agglomerated solvent, and does not contain coloured blister polymeric beads.
2. coating composition according to claim 1, wherein actual pigment volume content and any difference a) and b) between total amount are made up of other non-opacifying property extender particles.
3. coating composition according to claim 1, wherein said opacifying property pigment particles is white.
4. coating composition according to claim 2, wherein said opacifying property pigment particles is white.
5. coating composition according to claim 3, the opacifying property pigment particles of wherein said white is selected from titanium dioxide and hollow polymeric particle.
6. coating composition according to claim 4, the opacifying property pigment particles of wherein said white is selected from titanium dioxide and hollow polymeric particle.
7., according to the coating composition of any one of claim 1 to 6, wherein said hollow polymeric particle is polymeric hollow spheroid, and described polymeric hollow spheroid account for coating composition be less than 10 volume %.
8., according to the coating composition of any one of claim 1 to 6, wherein said non-opacifying property extender particles is selected from the group be made up of magnesium calcium carbonate, calcium carbonate, nepheline syenite and kaolin.
9., according to the coating composition of any one of claim 1 to 6, wherein polymer binder particle has the FoxTg calculated value of 6 to 21 DEG C.
10., according to the coating composition of any one of claim 1 to 6, wherein said polymer binder particle is derived from vinylbenzene, butyl acrylate and vinylformic acid.
11. according to the coating composition of any one of claim 1 to 6, wherein said polymer binder particle accounts for 5 to 20 volume % of dry coating.
12. according to the coating composition of any one of claim 1 to 6, the acid number of wherein said polymer binder particle is 15 to 60mgKOH/g polymkeric substance.
13. according to the coating composition of any one of claim 1 to 6, wherein by the acid functional monomer being selected from vinylformic acid, methacrylic acid, toxilic acid or its acid anhydride being copolymerized in polymer binder particle the acid number changing described polymer binder particle.
14. according to the coating composition of any one of claim 1 to 6, wherein by following method or its equivalent method assessment dispersion agent demand: i) dispersion agent is added to gradually in the water dispersion of non-polymeric opacifying property pigment and extender particles, and the viscosity of monitoring gained mixture is to determine MV minium viscosity, and ii) amount for reaching the dispersion agent that MV minium viscosity is added is defined as dispersion agent demand.
15. according to the coating composition of any one of claim 1 to 6, and based on described water-based paint compositions, it contains the fugitive agglomerated solvent of maximum 4 % by weight.
16. according to the coating composition of any one of claim 1 to 6, and the FoxTg calculated value of polymer binder is down to-10 to-80 DEG C by wherein said fugitive agglomerated solvent.
17. according to the coating composition of any one of claim 1 to 6, and further containing coloured pigment.
18. according to the coating composition of any one of claim 1 to 6, and is using m and C according to following table criticalduring calculating, there is when dry the color meeting following standard
C*<C criticalwith
Y>mC*+35
19. coating compositions according to claim 18, have the C* value being less than 5 and the Y value being greater than 85.
20. according to the coating composition of any one of claim 1 to 6, and have 85 ° measure time be less than 15% glossiness.
21. have the goods on surface or the method for structure with the composition coating as described in any one of claim 1 to 20, comprise the steps: in the mode of at least one liquid level by coating described in brush, roller, pad or spray application; Make the drying of described liquid level and/or sclerosis.
22. goods, it has by the surface of the composition coating such as described in any one of claim 1 to 20.
23. structures, it has by the surface of the composition coating such as described in any one of claim 1 to 20.
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US8362132B2 (en) 2013-01-29
AR081183A1 (en) 2012-07-04
AU2011246490A1 (en) 2012-10-11
DK2386609T3 (en) 2013-09-23
US20110318594A1 (en) 2011-12-29

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